EP0526237A1 - Informationsverarbeitungsapparat sowie Elektroden-Substrat und im Apparat verwendetes Informationsaufnahmemedium - Google Patents

Informationsverarbeitungsapparat sowie Elektroden-Substrat und im Apparat verwendetes Informationsaufnahmemedium Download PDF

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EP0526237A1
EP0526237A1 EP92307006A EP92307006A EP0526237A1 EP 0526237 A1 EP0526237 A1 EP 0526237A1 EP 92307006 A EP92307006 A EP 92307006A EP 92307006 A EP92307006 A EP 92307006A EP 0526237 A1 EP0526237 A1 EP 0526237A1
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Prior art keywords
medium
electrode
substrate
information
recording medium
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EP92307006A
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French (fr)
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EP0526237B1 (de
Inventor
Ken C/O Canon Kabushiki Kaisha Eguchi
Haruki C/O Canon Kabushiki Kaisha Kawada
Kiyoshi C/O Canon Kabushiki Kaisha Takimoto
Toshihiko C/O Canon Kabushiki Kaisha Takeda
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0009—RRAM elements whose operation depends upon chemical change
    • G11C13/0014—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/005—Epitaxial layer growth
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B9/00—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor
    • G11B9/12—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor
    • G11B9/14—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor using microscopic probe means, i.e. recording or reproducing by means directly associated with the tip of a microscopic electrical probe as used in Scanning Tunneling Microscopy [STM] or Atomic Force Microscopy [AFM] for inducing physical or electrical perturbations in a recording medium; Record carriers or media specially adapted for such transducing of information
    • G11B9/1463—Record carriers for recording or reproduction involving the use of microscopic probe means
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B9/00—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor
    • G11B9/12—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor
    • G11B9/14—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor using microscopic probe means, i.e. recording or reproducing by means directly associated with the tip of a microscopic electrical probe as used in Scanning Tunneling Microscopy [STM] or Atomic Force Microscopy [AFM] for inducing physical or electrical perturbations in a recording medium; Record carriers or media specially adapted for such transducing of information
    • G11B9/1463—Record carriers for recording or reproduction involving the use of microscopic probe means
    • G11B9/1472—Record carriers for recording or reproduction involving the use of microscopic probe means characterised by the form

Definitions

  • the present invention relates to an information processing apparatus utilizing the principle of a scanning tunneling microscope (hereinafter abbreviated as "STM”), and an electrode substrate and an information recording medium used in the apparatus.
  • STM scanning tunneling microscope
  • memory materials are being used in computers and apparatuses related thereto, video discs, digital audio discs, etc., equipment constituting the nucleus of the electronics industry.
  • the development of new materials in this field is being very actively promoted.
  • the characteristics required of memory material vary in accordance with the use for which it is intended. The following are characteristics generally required of memory materials:
  • an STM a scanning tunneling microscope
  • G.Binning et al., Phys. Rev Let., 49,57 (1982) With this microscope, it is possible to perform high-resolution measurement on a real image in space, whether it is monocrystalline or amorphous. Further, it has an advantage that it allows the specimen to be observed with low power without being damaged by electric current. Moreover, it can operate even in ambient atmosphere so that it can be used with respect to various types of materials. Thus, a wide range of applications are expected from the STM.
  • the STM utilizes the fact that a tunnel current flows when a metal probe (a probe electrode) is brought near a conductive substance, up to a distance of approximately 1nm, while applying a voltage between them.
  • This current is very sensitive to changes in the distance between the metal probe and the conductive substance, and even allows for the reading of a variety of information regarding the entire electron cloud in an actual space by performing scanning with the probe in such a way as to maintain the tunnel current constant.
  • the resolution in the in-plane dimension is approximately 0.1nm.
  • a material having a memory effect with respect to voltage/current switching characteristics for example, a thin-film layer of a ⁇ -electron -type organic compound, chalcogen compound or the like, is used as the recording layer to perform recording and reproduction with an STM (Japanese Patent Laid-Open Publication Nos. 63-161552 and 63-161553). Assuming that the recording bit size is 10nm, this method makes it possible to perform recording and reproduction by as much as 1012bit/cm2.
  • Fig. 8 shows a sectional view of a conventional recording medium together with the tip of a probe electrode 202.
  • Numeral 101 indicates a substrate; numeral 102, an electrode layer; numeral 103, a recording layer; numeral 104, a track; numeral 202, the probe electrode; numeral 401, a data bit recorded on the recording layer 103; and numeral 402, crystal grains generated during the formation of the electrode layer 102.
  • the electrode layer 102 is formed by a usual method, such as vacuum evaporation or sputtering, the size of the crystal grains 402 ranges from approximately 30 to 50nm.
  • the distance between the probe electrode 202 and the recording layer 103 can be kept constant through a conventionally well-known circuit construction. That is, a tunnel current flowing between the probe electrode and the recording layer is detected, and its value is transmitted through a logarithmic compressor 302 and a low-pass filter 303 and then compared with a reference voltage. A Z-axis actuator 204 supporting the probe electrode is controlled in such a way that this comparison value approaches zero, thereby maintaining a constant distance between the probe electrode and the recording layer.
  • Fig. 9 shows a signal strength spectrum with respect to the signal frequency at point P at this time.
  • Any signals of a frequency component not higher than f0 are due to a gentle rise and fall of the substrate 101 caused by warp, distortion or the like.
  • the signals around f1 are due to surface irregularities of the electrode layer 103, caused mainly by the crystal grains 402 generated during the formation of the material into an electrode.
  • Symbol f2 indicates a recording data carrier component
  • numeral 403 indicates a data signal band as shown in Fig. 6.
  • Symbol f3 indicates a signal component generated from the atomic/molecular arrangement of the recording layer 103.
  • Symbol f T indicates a tracking signal, which enables the probe electrode 202 to trace data arrays. It can be realized by forming a groove on the medium or writing thereto a signal which enables detection whenever an off-track condition occurs.
  • an electrode substrate comprising a substrate and an electrode layer of a noble metal crystal formed on the substrate, the noble metal crystal exhibiting a substantially linear domain boundary and a plane orientation dispersion angle in X-ray analysis of 1°or less.
  • an information recording medium having an electrode layer according to the above first aspect, as a recording layer.
  • an information recording medium comprising a substrate, an electrode layer of a noble metal crystal formed on the substrate, and a recording layer provided on the electrode layer, the noble metal crystal exhibiting a substantially linear domain boundary and a plane orientation dispersion angle in X-ray analysis of 1° or less.
  • an information processing apparatus comprising: an information recording medium according to the present invention as described above; a probe electrode arranged in close proximity to this medium; and a voltage applying circuit for applying a pulse voltage between the medium and the probe electrode, information being written onto the medium by the application of the pulse voltage; an information processing apparatus comprising: an information recording medium according to the present invention as described above; a probe electrode arranged in close proximity to this medium; a first voltage applying circuit for applying a pulse voltage between the medium and the probe electrode, and a second voltage applying circuit for applying a bias voltage between the medium and the probe electrode, information being written onto the medium by the application of the pulse voltage and read from the medium by the application of the bias voltage; and an information processing apparatus comprising: an information recording medium according to the present invention as described above; a probe electrode arranged in close proximity to this medium; and a voltage applying circuit for applying a bias voltage between the medium and the probe electrode, information being read from the medium by the application of the bias voltage are provided.
  • an information processing method comprising the steps of: preparing an information recording medium according to the present invention as described above; arranging a probe electrode in close proximity to the medium; and applying a pulse voltage between the medium and the probe electrode so as to write information onto the medium; an information processing method comprising the steps of: preparing an information recording medium according to the present invention as described above; arranging a probe electrode in close proximity to the medium; applying a pulse voltage between the medium and the probe electrode so as to write information onto the medium; and applying a bias voltage between the medium and the probe electrode so as to read the information from the medium; and an information processing method comprising the steps of: preparing an information recording medium according to the present invention as described above; arranging a probe electrode in close proximity to the medium; and applying a bias voltage between the medium and the probe electrode so as to read information from the medium are provided.
  • the noble metal crystal of the electrode substrate is preferably a planar crystal forming a (111) plane orientation facet. Further, it is desirable that the noble metal crystal be one grown from a conductive substrate through a hole provided in an insulating layer formed on the conductive substrate.
  • the plane orientation dispersion angle of the planar crystal surface is preferably 0.6° or less
  • the aspect ratio of the noble metal crystal is 10 or more
  • the maximum surface irregularity in a 10 ⁇ m square i.e., a square area of 10 ⁇ m x 10 ⁇ m
  • the maximum surface irregularity in a 10 ⁇ m be 1nm or less and information be recorded by changes in the physical conditions of the recording layer, with the recording layer having an "electrical memory" effect.
  • the recording medium have a track, the recording layer consisting of a monomolecular film of an organic compound or a built-up film thereof, and the recording layer having an thickness ranging from 5 to 300 ⁇ , allowing repeated recording and erasing. Further, it is desirable that the recording layer be formed by the Langmuir-Blodgett's technique.
  • the term "electrical memory effect” means the following phenomenon:
  • the probe electrode have the same pattern as the specifiable pattern of the electrode substrate of the recording medium, and that the probe electrode be of a multi-probe type.
  • the present invention provides a substrate electrode having a smooth surface so as to make it possible to fully make use of the function of an information processing apparatus utilizing the principle of the STM.
  • the dispersion angle in (111) orientation is small, making it possible to obtain an electrode substrate having a dispersion angle of 1° or less.
  • the ratio of the maximum diameter of the (111) surface to the height of the planar crystal, i.e., the aspect ratio, of the gold crystal is approximately 30.
  • a gold crystal having an aspect ratio of 10 or more can be easily obtained, which is preferably used in the present invention. Under a still more preferable condition, a crystal having an aspect ratio of 100 or more can be obtained.
  • the above planar gold substrate can be formed by the following processes: First, I2 is dissolved in an oxidizing solution having the property to dissolve gold, for example, a KI aqueous solution, in order to obtain an iodine solution in which gold is dissolved to obtain a gold-complex aqueous solution (in which gold is dissolved as a complex having a structure of (AuI4) ⁇ ).
  • an oxidizing solution having the property to dissolve gold for example, a KI aqueous solution
  • an iodine solution in which gold is dissolved to obtain a gold-complex aqueous solution (in which gold is dissolved as a complex having a structure of (AuI4) ⁇ ).
  • a substrate is immersed in this gold-complex aqueous solution, and, to reduce the insolubility of the gold, the I2 is removed from the reaction system by evaporating the same by heating or reducing the I2 to I ⁇ by using a reducing agent, and the gold complex is disintegrated by heating or the like to cause it to crystallize on the surface of the substrate.
  • the rate of crystallization is high, a grain-cluster-like polycrystal will be generated.
  • the planar gold crystal is grown by an oxidizing dissolution reaction while balancing the etching rate with the disintegration rate of the complex. This process suggests a similarity to a vapor-phase epitaxial growth.
  • Fig. 4 shows an STM image of a (111) surface grown in the manner described above.
  • the STM image of a 1 ⁇ m square i.e., a square area of 1 ⁇ m x 1 ⁇ m
  • a substantially flat smooth electrode substrate has been realized in a 1 ⁇ m square area by using the gold crystal.
  • the irregularity profile in the Z-axis direction of Fig. 4(b) its surface irregularities consist of atomic-step-like long-period steps of 1nm or less. With this planar gold electrode, it is possible to provide an electrode substrate having a still higher level of smoothness.
  • the size of the planar gold crystal under the normal condition ranges from 1 ⁇ m square to 1mm square. Under optimum conditions, it is possible to obtain a crystal having a size of 10mm square or less, that is, several mm square. However, it is also possible for a crystal having a large size of 10mm square or more to be separated, which is controllable, though difficult. Further, it is also possible to prepare an electrode substrate by continuously forming minute planar crystals. Also, with such an electrode substrate it is possible to obtain an electrode substrate in which the (111) plane orientation dispersion angle is smaller than that of a substrate formed by a usual vacuum film formation method, thus making it possible to form an electrode having an excellent orientation property.
  • any material can be used for the substrate material as long as it does not cause a serious corrosion in the gold-complex solution.
  • the substrate material that can be used include: insulating materials such as mica, MgO, SiO2, and Si3N4; organic high-molecular weight materials; Si substrates (crystalline or amorphous), which are conductive materials; graphite (HOPG); and various metal substrates and substrates of compounds thereof.
  • planar crystal and the production method thereof have been described with reference to the case where gold is adopted as the material, the planar crystal to be grown is not restricted to a gold crystal.
  • a similar technique is also applicable to noble metal materials allowing the formation of a complex halide, such as Pt, Pd, Rh, and Ir. Further, it is also applicable to a complex cyanide and a complex sulfite.
  • Fig. 5 is a sectional view of a recording medium using an electrode substrate according to the present invention.
  • Numeral 101 indicates a substrate; numeral 102, an electrode layer having a smooth surface; numeral 103, a recording layer; numeral 104, a track; numeral 202, a probe electrode; and numeral 401, a data bit.
  • the recording layer may be formed of a material capable of developing a memory-switching phenomenon (an electrical memory effect) having current-voltage characteristics, as for example, an organic monomolecular film or a built-up film thereof, having molecules each including both a group having a ⁇ electron level and a group having a ⁇ electron level deposited only on the electrode. Due to the electrical memory effect, it is possible to reversibly effect transition (switching) between a low-resistance condition (ON condition) and a high-resistance condition (OFF condition) (the ON and OFF conditions in Fig.
  • a memory-switching phenomenon an electrical memory effect having current-voltage characteristics
  • each of the conditions can be maintained (stored in memory) without applying any voltage.
  • organic materials exhibit an insulating or semi-insulating property.
  • the organic materials that can be applied to the present invention which contain a group having a ⁇ electron level, include an extremely wide range.
  • a dye having a ⁇ electron system which is suitable for the present invention, include: dyes having a porphyrin skeleton, such as phthalocyanine and tetraphenylporphyrin; azulene-type dyes having a squalilium group and a croconic methine group as a bonding chain; dyes similar to a cyanine type or cyanine dyes in which two nitrogen-containing complex rings, such as quinoline, benzothiazole, or benzooxazole, are connected by a squalilium group and a croconic methine group; condensed polycyclic aromatic compounds, such as anthracene and pyrene; chain compounds formed by polymerization of an aromatic cyclic compound or a complex cyclic compound
  • a preferable film thickness is in the range of 5 to 300 ⁇ .
  • the recording layer 103 is not absolutely necessary. As stated in Phys. Rev. Lett ., 65, 2418 (1990) by H.J. Mamin et al., it is possible to directly cause a perturbation on the surface of the electrode layer 102 so as to selectively generate a disturbance thereon, for example, by depositing fine gold particles on the electrode surface through field evaporation of gold by using a gold probe electrode. According to the above reference, this field evaporation of gold varies somewhat depending upon the distance between the electrode surface and the tip of the probe electrode. With an application voltage of 3.2V or less, the probability that the field evaporation of gold will take place is zero.
  • the pulse width which allows recording at this time is 1 ⁇ m or less, making it possible to cope with high-speed recording.
  • the pit diameter varies depending upon various conditions. Usually, recording with a pit diameter of 100 to 300 ⁇ is possible, and under more preferable conditions, recording can be effected with a pit diameter of 30 to 100 ⁇ , and further, 30 to 70 ⁇ .
  • a grain cluster of 300 to 500 ⁇ is usually generated, so that it is rather difficult to clearly distinguish the recording from the surface irregularities on the electrode substrate. Therefore, in the present invention, use of a smooth electrode substrate according to the present invention is indispensable.
  • the direction of the field evaporation largely depends upon the surface condition of the smooth substrate electrode, and the above-described phenomenon occurs regardless of the polarity of the application electrode. That is, by making the polarity on the side of the probe electrode positive, deposition of fine gold particles takes place on the substrate electrode surface, as described above. If, conversely, a positive application is effected on the substrate electrode side, the deposition of gold on the substrate electrode surface takes place in the same way, although the threshold voltage thereof increases. However, it is also possible to position the probe electrode on a minute gold protrusion on the substrate electrode surface and remove the gold protrusion by applying a voltage (erasable).
  • Fig. 5 Although methods of directly imparting a perturbation to the electrode layer have been described, it is also possible, as shown in Fig. 5, to provide the recording layer 103 on a smooth electrode surface and selectively cause changes in the conditions of the recording layer, including changes in the configuration thereof, thereby effecting recording.
  • the material to be employed for the recording layer it is possible to use an organic compound which allows changes in configuration to take place through irradiation of various types of energy at low levels as described below. Further, by effecting recording through changes in the condition of individual organic molecules, it is possible to obtain a recording density on a molecular scale.
  • recording may be effected separately. Generally, however, it is often realized in the form of a combination of a number of effects.
  • the formation of the recording layer 103 may be effected by evaporation, the cluster ion beam method or the like.
  • the LB method is the most suitable of the conventional methods known in the art. With the LB method, a monomolecular film of an organic compound having in one molecule a hydrophobic portion and a hydrophilic portion, or a built-up film thereof, can be easily formed on a substrate, thereby making it possible to stably provide an organic ultra-thin film which has a thickness of a molecular order and which is uniform and homogeneous over a wide area. Accordingly, it is possible to prepare a recording medium which reflects the surface property of an under-coat electrode substrate as it is.
  • a monomolecular film or a built-up film thereof is formed by utilizing the fact that in molecules each having a structure in which hydrophilic and hydrophobic portions exist therein, an appropriate balance is maintained between them, the molecules form a monomolecular layer on a water surface, with the hydrophilic groups facing downwards.
  • the group constituting the hydrophobic portion include various types of hydrophobic groups, such as generally well-known saturated and unsaturated hydrocarbon groups, condensed polynuclear aromatic groups, and chain polycyclic phenyl groups. One, or a plurality of types of such groups, are combined to form the hydrophobic portion.
  • hydrophilic portion includes various types of hydrophilic groups, such as carboxyl group, ester group, acid amide group, imide group, hydroxyl group, and amino group (of first, second, third or fourth grade).
  • hydrophilic groups such as carboxyl group, ester group, acid amide group, imide group, hydroxyl group, and amino group (of first, second, third or fourth grade).
  • One, or a plurality of types of such groups, are combined to form the above-mentioned hydrophilic portion.
  • the tip of the probe electrode 202 must be as pointed as possible so that the resolution in recording and reproduction may be improved.
  • a probe electrode having an atomic resolution can be prepared by an electrolytic polishing method, such as the tungsten method.
  • an electrolytic polishing method such as the tungsten method.
  • a probe electrode prepared in this way has an atomic resolution.
  • the configuration and processing method of the probe electrode are not restricted to those described above.
  • Fig. 6 shows the signal frequency spectrum of a signal at point P in the information processing apparatus of the present invention shown in Fig. 7.
  • Fig. 7 shows an example of the construction of an information processing apparatus utilizing the principle of the STM, which will be described below with reference to the drawing.
  • Numeral 101 indicates a substrate; numeral 102, a metal electrode layer; and numeral 103, a recording layer.
  • Numeral 201 indicates an XY stage; numeral 202, a probe electrode; numeral 203, a support member for the probe electrode; numeral 204, a linear actuator for driving the probe electrode 204 in the Z-direction; numerals 205 and 206, linear actuators for driving the XY stage in the X- and Y-directions, respectively; and numeral 207, a pulse voltage circuit.
  • Numeral 301 indicates an amplifier for detecting a tunnel current flowing from the probe electrode to the electrode layer 102 by way of the recording layer 103.
  • Numeral 302 indicates a logarithmic compressor for converting a change in the tunnel current into a value which is proportional to the gap distance of the recording layer; and
  • numeral 303 indicates a low-pass filter for extracting surface irregularity components of the recording layer.
  • Numeral 304 indicates an error amplifier for detecting an error between a reference voltage V REF and the low-pass filter 303; and numeral 305 indicates a driver for driving the actuator 204.
  • Numeral 306 indicates a drive circuit for performing position control of the XY stage.
  • Numeral 307 indicates a high-pass filter for separating data components.
  • any signals of a frequency component not higher than f0 are due to a gentle rise and fall of the substrate 101 due to warp, distortion or the like.
  • Symbol f2 indicates a recording data carrier component
  • numeral 403 indicates a data signal band.
  • Symbol f3 indicates a signal component generated from the atomic/molecular arrangement of the recording layer
  • symbol f T indicates a tracking signal.
  • a signal around f1 is due to a slight irregularity of the surface of the electrode layer 102, i.e., the (111) surface. This irregularity is made equal to or smaller than the recording signal. In recording and reproduction utilizing the STM, the change in this irregularity approximately corresponds to five layers of electrode materials (1nm or less).
  • the size of the smooth surface of the surface of the recording layer 103 is 1 ⁇ m square. Under a more favorable condition, 10 ⁇ m or more. This provides the following advantages:
  • An iodine solution was prepared by dissolving 4g of potassium iodide (KI) and 0.6g of iodine (I2) in 50ml of pure water. Then, a 5000 ⁇ thick gold film formed by vacuum evaporation (approximately 0.08g in terms of weight) was completely dissolved in the iodine solution to obtain a gold/iodine-complex stock solution. 10ml of this stock solution was pipetted and diluted in 50ml of pure water to prepare a reaction mother liquor. A silicon substrate whose natural oxide film had been etched by hydrofluoric acid was immersed in the mother liquor and heated to 80°C on a hot plate.
  • KI potassium iodide
  • I2 iodine
  • a track 104 having a width of 0.1 ⁇ m, a pitch of 1.0 ⁇ m, and a depth of 50 ⁇ was formed on the surface of the flat gold crystal electrode by a focused ion beam.
  • the focused ion beam process was conducted by using gold ions under the following conditions: acceleration voltage: 40KV; ion current: 14pA; dose amount: 1.0 x 1016/cm2.
  • a four-layered polyimide LB film was formed on the smooth electrode substrate, prepared in the above-described manner, as the recording layer 103.
  • the recording layer 103 was formed by using the polyimide LB film as follows.
  • a polyamide acid as shown in formula (1) was dissolved in an N,N′-dimethylacetamide/benzene mixture solution of 1:1 (V/V) (density in terms of monomer: 1 x 10 ⁇ 3M). Then, it was mixed with a separately prepared 1 x 10 ⁇ 3M solution of N,N′-dimethyloctadecylamine in the same solvent in a proportion of 1:2 (V/V) to prepare a polyamide-acid-octadecylamine salt solution as shown in formula (2).
  • This solution was developed on a water phase consisting of pure water at a temperature of 20°C to form a monomolecular film on the surface of the water.
  • the surface pressure was augmented to 25 mN/m.
  • the above substrate electrode was gently immersed in such a way as to traverse the water surface at a rate of 5 mm/min, and was then pulled up gently at a rate of 5 mm/min to prepare a two-layered Y-type monomolecular built-up film. By repeating this operation, a four-layered monomolecular built-up film of polyamide-acid-octadecylamine salt was formed.
  • this substrate was calcinated by heating for thirty minutes at 200°C under a reduced pressure ( ⁇ 1 mmHg) to imidize the polyamide-acid-octadecylamine salt (Formula 3), thereby obtaining a four-layered polyimide monomolecular built-up film.
  • the surface configuration of a recording medium prepared in the above-described manner was examined on the information processing apparatus shown in Fig. 7. Upon examination, it was found that the surface of the recording medium reflected the smoothness of the electrode and the track 104. In a 10 ⁇ m square, the track 104 had been formed to a depth of 50 ⁇ , and, outside the track 104, the maximum surface irregularity was 0.9nm, with the dispersion peak being 0.4nm. Accordingly, the track 104 could be clearly distinguished.
  • a platinum/rhodium probe electrode 202 was used as the probe electrode 202.
  • the probe electrode 202 is used for the purpose of controlling the distance (Z) between it and the recording layer 103, and is under a fine current control to a constant level.
  • the linear actuators 204, 205 and 206 are designed such that they allow fine control also in the in-plane (X, Y) directions while keeping the distance Z constant.
  • the probe electrode 202 is capable of directly effecting recording, reproduction and erasing. Additionally, the recording medium is placed on the high-precision XY stage 201 and can be moved to an arbitrary position.
  • the recording layer 103 comprising a four-layered polyimide film as described above, was placed on the XY stage 201. Then, a voltage of +1.5V was applied between the probe electrode 202 and the electrode layer 102 of the recording medium, and the distance (Z) between the probe electrode 202 and the surface of the recording layer 103 was adjusted while monitoring the current. At this time, a probe current Ip for controlling the distance Z between the probe electrode 202 and the surface of the recording medium was set in such a way that 10 ⁇ 10A ⁇ Ip ⁇ 10 ⁇ 11A.
  • the probe electrode 202 was positioned on the + side and the electrode layer 102 on the - side, applying a rectangular pulse voltage beyond a threshold voltage V th ON causing the electric memory material (the four-layered polyimide film) to be changed to a low-resistance condition (ON condition). Afterwards, the probe electrode 202 was brought back to the recording start point, and was caused to scan the recording layer 103 again. Here, adjustment was made in such a way that Z was constant at the time of reading of the recorded information. As a result, it was shown that in the recording bit, a probe current of approximately 10nA flowed, under the ON condition.
  • the probe voltage was set at 10V which is above the threshold voltage V th OFF causing the electric memory material to change from the ON to the OFF condition.
  • the recording position was traced again to confirm that this caused the entire recording conditions to be erased, thereby causing the material to be changed to the OFF condition.
  • a recording pulse was applied in accordance with the above recording method to a position which was in the OFF condition with the recording condition erased to confirm that it caused the material to be changed to the OFF condition. It was also confirmed that the recording condition could be erased again.
  • Example 1 Using the mother liquor described in Example 1, electrode layers were formed on different types of substrates, and an experiment similar to that of Example 1 was conducted thereon. Table 1 shows the surface properties of the electrode layers used in the experiment.
  • Example 1 A planar gold crystal like that of Example 1 was formed under the same experimental conditions as in Example 1 except that instead of taking the iodine out of the reaction system by sublimation, the iodine was reduced by using reducing agents.
  • the reducing agents used in the experiment were sulfite ions and hydroquinone.
  • the substrate was a silicon substrate and the crystallization temperature was 60°C.
  • Example 2 An experiment was conducted in which the gold concentration of the stock solution of Example 1 and the crystallization temperature were varied. The results are summarized in Table 2.
  • the substrate used was a silicon crystal substrate.
  • a silicon substrate and a glass (SiO2) substrate which had been surface-processed by various well-known methods in such a manner that the matrix intersections at intervals of 500 ⁇ m were made 1 ⁇ m to 2 ⁇ m square were immersed in the mother liquor used in Example 1 to observe how crystallization took place under the same conditions as in Example 1.
  • Each of the seed substrates for selective deposition used in the experiment was prepared in the following manner:
  • Example 2 four layers of polyimide monomolecular films were accumulated on an electrode substrate prepared by the method 5 to form a recording medium, which was examined for surface configuration on the information processing apparatus shown in Fig. 7.
  • the surface of the recording medium reflected the smoothness of the electrode, and the maximum surface irregularity in a 10 ⁇ m square was 0.9nm or less, with the dispersion peak being 0.4nm or less.
  • the planar gold crystal selectively deposited formed a (111) plane orientation facet, which was in the same pattern as the seed pattern used. Further, the edges of the facet reflected the characteristics of the crystal surface so as to provide a track of a very high degree of linearity (see Fig. 12). The track groove formed was deep, so that the track could be clearly distinguished as in Example 1.
  • Example 1 An experiment was performed on recording, reproduction and erasing, and it was confirmed that recording, reproduction and erasing could be performed as in Example 1 with an electrode substrate prepared in the above-described manner. Further, it was also confirmed that recording, reproduction and erasing could be performed with electrode substrates prepared by other methods as described above.
  • Example 6 a selective deposition of gold as shown in Example 6 is also possible with a combination of the selective deposition according to the method of Example 5 and the crystal growth process shown in Example 1.
  • a track 104 having a width of 0.1 ⁇ m, a pitch of 1.0 ⁇ m and a depth of 5.0 ⁇ was formed on the surface of the planar gold crystal electrode by a focused ion beam, using gold ions under the following conditions: acceleration voltage: 40KV; ion current: 14pA; and dose amount: 1.0 x 1016/cm2.
  • a gold wire having a diameter of 250 ⁇ m was formed into a gold chip through electrolytic polishing in concentrated hydrochloric acid (1.5 to 2 Vdc), thereby preparing a gold probe electrode 202, which was used in an experiment on recording and reproduction.
  • the probe electrode 202 is intended for the control of the distance (Z) between it and the recording layer 103, and is under a fine current control to attain a constant level. Further, the linear actuators 204, 205 and 206 are so designed as to allow fine motion control in the in-plane directions (X, Y) while maintaining the distance Z constant.
  • the probe electrode 202 is capable of directly performing recording, reproduction and erasing. Moreover, the recording medium is placed on the high-precision XY stage 201 and can be moved to an arbitrary position.
  • the above-mentioned gold substrate electrode was placed on the XY stage 201. Then, a voltage of +1.5V was applied between the probe electrode 202 and the gold substrate electrode 102, and the distance (Z) between the probe electrode 202 and the recording medium 103 was adjusted while monitoring the current.
  • a setting was made in such a manner that the probe current I p for controlling the distance Z between the probe electrode 202 and the surface of the recording medium 103 was kept in the range: 10 ⁇ 10A ⁇ Ip ⁇ 10 ⁇ 11A.
  • a gold substrate electrode was formed in the same manner as in Example 7.
  • a two-layered spiropyran LB film was formed on the prepared gold substrate electrode, thereby preparing the recording layer 103.
  • a description will be given on how the recording layer 103 using the spiropyran LB film was formed.
  • a mixture solution of a spiropyran derivative with an octadecyl group introduced therein and arachidic acid in the proportion of 1 : 2 (solvent: chloroform in a concentration of 1 x 10 ⁇ 3M) was developed on a water phase consisting of an aqueous solution of CdCl2 (concentration: 1 x 10 ⁇ 4M) at a temperature of 20°C to form a monomolecular film on the water surface.
  • the surface pressure was raised up to 30 mN/m. While keeping the surface pressure constant, the above substrate electrode was gently immersed in such a way as to traverse the water surface at a rate of 5 mm/min. Then, it was gently pulled up, thereby forming a two-layered Y-type monomolecular built-up film.
  • Example 7 Using the mother liquor described in Example 7, electrode layers were formed on various types of substrates, and an experiment similar to that of Example 7 was conducted. The surface properties of the electrode layers used in the experiment are summarized in Table 1 (shown above).
  • Example 7 the surface of each recording medium reflected the smoothness of the electrode and the track 104.
  • the track 104 had been formed 50 ⁇ deep, and the maximum surface irregularity outside the track 104 was 0.9nm or less, with the dispersion peak being 0.4nm or less. Therefore, as in Example 7, the track 104 could be clearly distinguished.
  • an experiment was conducted on recording, reproduction and erasing. It was confirmed that recording, reproduction and erasing could be performed as in Example 7.
  • Example 7 Further, a recording/reproduction experiment similar to that of Example 7 was performed using a spiropyran LB film as the recording layer, as in Example 8, and it was confirmed that recording and reproduction could be performed as in Example 7. Also, the average bit diameter was substantially the same value.
  • a silicon substrate and a glass (SiO2) substrate which had been surface-processed by various well-known methods in such a way as to make the matrix intersections at intervals of 500 ⁇ m 1 ⁇ m to 2 ⁇ m square were immersed in the mother liquor used in Example 7 to observe how crystallization occurred under the same conditions as in Example 7.
  • Each of the seed substrates for selective deposition used in the experiment was prepared in the following manner:
  • an electrode substrate prepared by the method 5 was examined for surface configuration on the information processing apparatus shown in Fig. 7.
  • the maximum surface irregularity in a 10 ⁇ m square was 0.9nm or less, with the dispersion peak being 0.4nm or less.
  • Example 7 An experiment was performed on recording, reproduction and erasing, and it was confirmed that recording, reproduction and erasing could be performed as in Example 7. Further, it was also confirmed that recording, reproduction and erasing could be performed with electrode substrates prepared by other methods as described above.
  • the present invention provides the following advantages:
  • an electrode substrate according to the present invention is formed by using an Si chip as a substrate which is prepared by incorporating therein a writing/reading control circuit, whereby it is possible to provide a memory medium comprising a writing/reading control circuit and a recording medium, which are formed as one integral unit.

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  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Semiconductor Memories (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
EP92307006A 1991-07-31 1992-07-30 Informationsverarbeitungsapparat sowie Elektroden-Substrat und im Apparat verwendetes Informationsaufnahmemedium Expired - Lifetime EP0526237B1 (de)

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EP0803702A2 (de) * 1996-04-25 1997-10-29 Hewlett-Packard Company Mikro-Nadel für Probe-Apparat
US6110579A (en) * 1996-12-17 2000-08-29 Canon Kabushiki Kaisha Recording medium used in information processing apparatus using probe
WO2007096359A2 (en) * 2006-02-21 2007-08-30 International Business Machines Corporation Method for high density data storage and imaging

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US5495109A (en) * 1995-02-10 1996-02-27 Molecular Imaging Corporation Electrochemical identification of molecules in a scanning probe microscope
US7260051B1 (en) 1998-12-18 2007-08-21 Nanochip, Inc. Molecular memory medium and molecular memory integrated circuit
US6500510B1 (en) 1999-11-04 2002-12-31 Molecular Storage Technologies, Inc. Molecular level optical information storage devices
US6849085B2 (en) 1999-11-19 2005-02-01 Advanced Bio Prosthetic Surfaces, Ltd. Self-supporting laminated films, structural materials and medical devices manufactured therefrom and method of making same
US7736687B2 (en) 2006-01-31 2010-06-15 Advance Bio Prosthetic Surfaces, Ltd. Methods of making medical devices
US7235092B2 (en) * 1999-11-19 2007-06-26 Advanced Bio Prosthetic Surfaces, Ltd. Guidewires and thin film catheter-sheaths and method of making same
US10172730B2 (en) * 1999-11-19 2019-01-08 Vactronix Scientific, Llc Stents with metallic covers and methods of making same
US6379383B1 (en) 1999-11-19 2002-04-30 Advanced Bio Prosthetic Surfaces, Ltd. Endoluminal device exhibiting improved endothelialization and method of manufacture thereof
US8458879B2 (en) * 2001-07-03 2013-06-11 Advanced Bio Prosthetic Surfaces, Ltd., A Wholly Owned Subsidiary Of Palmaz Scientific, Inc. Method of fabricating an implantable medical device
US7195641B2 (en) 1999-11-19 2007-03-27 Advanced Bio Prosthetic Surfaces, Ltd. Valvular prostheses having metal or pseudometallic construction and methods of manufacture
US6537310B1 (en) 1999-11-19 2003-03-25 Advanced Bio Prosthetic Surfaces, Ltd. Endoluminal implantable devices and method of making same
WO2001055473A1 (en) * 2000-01-25 2001-08-02 Boston Scientific Limited Manufacturing medical devices by vapor deposition
US6695865B2 (en) 2000-03-20 2004-02-24 Advanced Bio Prosthetic Surfaces, Ltd. Embolic protection device
US8845713B2 (en) 2000-05-12 2014-09-30 Advanced Bio Prosthetic Surfaces, Ltd., A Wholly Owned Subsidiary Of Palmaz Scientific, Inc. Self-supporting laminated films, structural materials and medical devices manufactured therefrom and methods of making same
US7233517B2 (en) 2002-10-15 2007-06-19 Nanochip, Inc. Atomic probes and media for high density data storage
AT500259B1 (de) * 2003-09-09 2007-08-15 Austria Tech & System Tech Dünnschichtanordnung und verfahren zum herstellen einer solchen dünnschichtanordnung
US7420106B2 (en) * 2005-03-18 2008-09-02 The University Of Utah Research Foundation Scanning probe characterization of surfaces
US7367119B2 (en) 2005-06-24 2008-05-06 Nanochip, Inc. Method for forming a reinforced tip for a probe storage device
US7463573B2 (en) 2005-06-24 2008-12-09 Nanochip, Inc. Patterned media for a high density data storage device
US20070041237A1 (en) * 2005-07-08 2007-02-22 Nanochip, Inc. Media for writing highly resolved domains
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EP0803702A2 (de) * 1996-04-25 1997-10-29 Hewlett-Packard Company Mikro-Nadel für Probe-Apparat
EP0803702A3 (de) * 1996-04-25 1998-04-15 Hewlett-Packard Company Mikro-Nadel für Probe-Apparat
US5953306A (en) * 1996-04-25 1999-09-14 Hewlett-Packard Company Micro needle probe apparatus having probes cantilevered over respective electronic circuits, moving medium memory device including same and method of making same
US6110579A (en) * 1996-12-17 2000-08-29 Canon Kabushiki Kaisha Recording medium used in information processing apparatus using probe
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WO2007096359A3 (en) * 2006-02-21 2008-01-10 Ibm Method for high density data storage and imaging

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JP2981804B2 (ja) 1999-11-22
EP0526237B1 (de) 1998-04-08
DE69225032T2 (de) 1998-08-13
CA2074914A1 (en) 1993-02-01
US5329514A (en) 1994-07-12
CA2074914C (en) 1997-12-02
ATE164963T1 (de) 1998-04-15
DE69225032D1 (de) 1998-05-14

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